Method of producing an encapsulated hydroprocessing catalyst

ABSTRACT

Embodiments of the present disclosure are directed to a method of producing an encapsulated hydroprocessing catalyst comprising: preparing a hydroprocessing catalyst comprising a porous support and at least one metal supported on the porous support, the porous support comprising alumina, silica, titania, or combinations thereof, and the at least one metal selected from IUPAC Groups 6, 9 and 10 metals; applying a catalyst activation precursor comprising a sulfur containing compound, a catalyst deactivation precursor comprising a nitrogen containing compound, or both onto pores of the hydroprocessing catalyst to form a loaded hydroprocessing catalyst; and coating the loaded hydroprocessing catalyst with a coating material to produce the encapsulated hydroprocessing catalyst, wherein the coating material comprises a polymer or a paraffinic oil.

TECHNICAL FIELD

Embodiments of the present disclosure generally relate to methods ofproducing an encapsulated hydroprocessing catalyst.

BACKGROUND

Hydroprocessing catalysts are used in the removal of impurities fromhydrocarbon feedstocks that are typically derived from the distillationof crude petroleum. Common impurities are sulfur compounds and nitrogencompounds. These impurities are catalytically converted into hydrogensulfide and ammonia to then are subsequently removed from thehydrocarbon feedstocks.

Generally, hydroprocessing catalysts are composed of a support with ametal, such as molybdenum, tungsten, nickel, and cobalt, depositedthereon. The conventional methods for preparing these hydroprocessingcatalysts are characterized in that a support composited with the metalcomponents, for example by impregnation. These metal components are onlyactive when they are in a sulfide form. Thus, the hydroprocessingcatalysts generally are subjected to a sulfidation treatment.

Conventional sulfidation treatments are ex-situ and in-situsulfidations. Ex-situ sulfidation processes take place outside a reactorin which the catalyst is to be used in hydroprocessing hydrocarbonfeedstocks. In such a process, the catalyst is contacted with a sulfurcompound (catalyst activation precursor) outside the reactor and themetal is converted into the metal sulfide. In-situ sulfidation processestake place in the reactor in which the catalyst is to be used inhydroprocessing hydrocarbon feeds. Here, the catalyst is contacted inthe reactor at elevated temperature with a hydrogen gas stream mixedwith a sulfiding agent (catalyst activation precursor), and the metal isconverted into the metal sulfide. In these ex-situ and in-situsulfidations, the catalyst activation precursor is required to activatethe metal components in the catalyst.

SUMMARY

Accordingly, there is a continual need for hydroprocessing catalystswith improved catalytic activity while avoiding excess supply ofcatalyst activation precursor and catalyst deactivation precursor.Embodiments of the present disclosure meet this need by encapsulating acatalyst activation precursor, a catalyst deactivation precursor, orboth onto pores of hydroprocessing catalysts through the coating layer.This eliminates or greatly reduces the need for bringing catalystactivation precursor and catalyst deactivation precursor into a refineryprocess.

According to one or more aspects of the present disclosure, a method ofproducing an encapsulated hydroprocessing catalyst may comprisepreparing a hydroprocessing catalyst comprising a porous support and atleast one metal supported on the porous support, the porous supportcomprising alumina, silica, titania, or combinations thereof, and the atleast one metal selected from International Union of Pure and AppliedChemistry (IUPAC) Groups 6, 9 and 10 metals; applying a catalystactivation precursor comprising a sulfur containing compound, a catalystdeactivation precursor comprising a nitrogen containing compound, orboth onto pores of the hydroprocessing catalyst to form a loadedhydroprocessing catalyst; and coating the loaded hydroprocessingcatalyst with a coating material to produce the encapsulatedhydroprocessing catalyst, wherein the coating material comprises apolymer or a paraffinic oil.

Additional features and advantages of the described embodiments will beset forth in the detailed description which follows, and in part will bereadily apparent to those skilled in the art from that description orrecognized by practicing the described embodiments, including thedetailed description which follows and the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The following detailed description of specific embodiments of thepresent disclosure can be best understood when read in conjunction withthe drawings enclosed herewith.

FIG. 1 schematically depicts a generalized flow diagram of a method forproducing encapsulated hydroprocessing catalyst, according to one ormore embodiments of the present disclosure;

FIG. 2 schematically depicts a generalized flow diagram of anotherembodiment of a method for producing encapsulated hydroprocessingcatalyst, according to one or more embodiments of the presentdisclosure;

FIG. 3 is a thermogravimetric analysis (TGA) of Example 3; and

FIG. 4 is a TGAs of Example 6 and Example 8.

Reference will now be made in detail to various embodiments, someembodiments of which are illustrated in the accompanying drawings.

DETAILED DESCRIPTION

As used in this disclosure, a “catalyst” refers to any substance whichincreases the rate of a specific chemical reaction. Catalysts describedin this disclosure may be utilized to promote various reactions, suchas, but not limited to, hydrocracking, hydrodemetalization,hydrodesulfurization, hydrodenitrogenation, hydrogenation, orcombinations thereof. As used in this disclosure, “cracking” generallyrefers to a chemical reaction where a molecule having carbon-to-carbonbonds is broken into more than one molecule by the breaking of one ormore of the carbon-to-carbon bonds, or is converted from a compoundwhich includes a cyclic moiety, such as an aromatic, to a compound whichdoes not include a cyclic moiety. “Hydrocracking” refers to the crackingof hydrocarbons in the presence of hydrogen.

As used in this disclosure, “catalytic activity” with respect to thehydroprocessing catalyst refers to the ability of the hydroprocessingcatalyst to catalyze hydroprocessing reactions, such as hydrocrackingreactions, hydrodemetalization reactions, hydrodesulfurizationreactions, hydrodenitrogenation reactions, hydrogenations reactions,etc.

As used in this disclosure, a “loaded hydroprocessing catalyst” refersto a catalyst including the hydroprocessing catalyst and the catalystactivation agent, the catalyst deactivation agent, or both onto pores ofthe hydroprocessing catalyst.

As used in this disclosure, a “polymer” refers to a polymeric compoundprepared by polymerizing monomers, whether of the same or a differenttype.

Coated Hydroprocessing Catalyst

Embodiments of the present disclosure are directed to coatedhydroprocessing catalysts. The coated hydroprocessing catalyst of thepresent disclosure may include a hydroprocessing catalyst comprising aporous support and at least one metal supported on the porous support;wherein the porous support comprising alumina, silica, titania, orcombinations thereof; and the at least one metal selected fromInternational Union of Pure and Applied Chemistry (IUPAC) Groups 6, 9and 10 metals; a catalyst activation agent, a catalyst deactivationagent, or both loaded onto pores of the porous support, the catalystactivation agent comprising at least one sulfur compound and thecatalyst deactivation agent comprising at least one nitrogen compound;and a coating layer on a surface of the hydroprocessing catalyst, thecoating layer encapsulating the catalyst activation agent, the catalystdeactivation agent, or both within the hydroprocessing catalyst, whereinthe coating layer comprises polymer, paraffinic oil, or both. Withoutbeing bound by theory, encapsulating the hydroprocessing catalyst with acoating layer reduces the need for supplemental catalyst deactivationagent, because the coating layer slows the desorption or decompositionof the catalyst deactivation agent loaded on the porous support.

As stated previously, the coated hydroprocessing catalyst includes thehydroprocessing catalyst. The hydroprocessing catalyst may include theporous support and the at least one metal.

The porous support may include alumina (Al₂O₃), silica (SiO2), titania(TiO₂), zeolite, or combinations thereof. In one or more embodiments,the porous support may include a zeolite. As used herein, a “zeolite”refers to a microporous, crystallized aluminosilicate material. Zeolitesof the present disclosure may have a FAU, MFI, MOR, or BEA typeframework as defined by International Zeolite Association (IZA)Structure Commission In one or more embodiments, the porous support mayinclude alumina (Al₂O₃), silica (SiO2), titania (TiO₂), or combinationsthereof. The porous support may have a molar ratio of alumina to silicaalumina-to-silica of from 5 to 1000, from 5 to 500, from 5 to 300, from5 to 200, from 5 to 100, from 2 to 1000, from 2 to 500, from 2 to 300,from 2 to 200, from 2 to 100, from 1 to 1000, from 1 to 500, from 1 to300, from 1 to 200, or from 1 to 100.

The porous support may have a pore volume of from 0.4 ml/g to 1.5 ml/g,from 0.4 ml/g to 1.25 ml/g, from 0.4 ml/g to 1.0 ml/g, from 0.4 ml/g to0.75 ml/g, or from 0.4 ml/g to 0.5 ml/g. The pore volume of the poroussupport may be measured by Brunauer, Emmett, and Teller (“BET”) method,which measures the quantity of nitrogen adsorbed on the support.

The porous support may have a surface area of up to 1000 square metersper gram (m²/g), or from 100 m²/g to 1000 m²/g, from 100 m²/g to 900m²/g, from 100 m²/g to 800 m²/g, from 100 m²/g to 500 m²/g, from 120m²/g to 1000 m²/g, from 120 m²/g to 900 m²/g, from 120 m²/g to 800 m²/g,from 120 m²/g to 500 m²/g, from 150 m²/g to 1000 m²/g, from 150 m²/g to900 m²/g, from 150 m²/g to 800 m²/g, from 150 m²/g to 500 m²/g, from 180m²/g to 1000 m²/g, from 180 m²/g to 900 m²/g, from 180 m²/g to 800 m²/g,from 180 m²/g to 500 m²/g, from 200 m²/g to 1000 m²/g, from 200 m²/g to900 m²/g, from 200 m²/g to 800 m²/g, or from 200 m²/g to 500 m²/g. Thebinder may have a surface area of from 100 m²/g to 200 m²/g, from 100m²/g to 150 m²/g, or from 150 m²/g to 200 m²/g.

The porous support may have an average pore size of from 10 Angstrom (Å)to 10,000 Å, from 10 Å to 9000 Å, from 10 Å to 8000 Å, from 10 Å to 5000Å, from 50 Å to 10000 Å, from 50 Å to 9000 Å, from 50 Å to 8000 Å, from50 Å to 5000 Å, from 100 Å to 10000 Å, from 100 Å to 9000 Å, from 100 Åto 8000 Å, from 100 Å to 5000 Å. The average pore sizes may becalculated by the equation Ps=4V/S, where Ps=pore size, V=pore volume,and S=surface area.

The porous support may be formed into the shape selected from the groupof sphere, cylinder, trilobe, twisted trilobe, and quadra-lobes. Methodsfor shaping the porous support may include, for example, extrusion,spray drying, pelletizing, agglomeration, oil drop, and the like. Asused herein, an “oil drop” process refers to precipitation that occursupon the pouring of a liquid into an immiscible liquid.

As stated above, the at least one metal may be supported on the poroussupport. The at least one metal may include the IUPAC Groups 6, 9 and 10metals. In some embodiments, the IUPAC Groups 6, 9 and 10 metals mayinclude Co, Mo, Ni, W, or combinations thereof. In one embodiment, theat least one metal may be in oxide form, such as CoO, MoO₃, NiO, WO₃. Inother embodiments, the at least one metal may be in sulfide form, suchas Co₉S₈, MoS₂, Ni₃S₂, WS₂.

The hydroprocessing catalysts may be bi-functional catalysts, havingboth a cracking function and a hydrogenation function. The crackingfunction may be provided by cracking components, such as zeolite,alumina, silica, or titania. The hydrogenation function may be providedby the at least one metal including the IUPAC Groups 6, 9 and 10 metals.In some embodiments, the at least one metal may be added to the poroussupport by mixing or impregnation. For example, the IUPAC Groups 6, 9and 10 metals may be introduced to the porous support by mixing, and maybe converted to an oxide in-situ by calcination.

The hydroprocessing catalyst may be used as catalysts forhydroprocessing reactions. Example hydrocarbon feedstocks that may beprocessed by the hydroprocessing catalysts presently described includecrude oil fractions such as naphtha, diesel, vacuum gas oil, vacuumresidue or intermediate refinery streams such as deasphalted oil, cokernaphtha, gas oils, and fluid catalytic cracking cycle oils. Inhydroprocessing reactions, the major reactions may be sulfur, nitrogen,and metal removal. The hydroprocessing catalysts may have one or more ofhydrodesulfurization (HDS), hydrodenitrogenation (HDN), orhydrodemetallization (HDM), hydrocracking (HCR), hydrogenation (HYD)functionality.

In one or more embodiments, the hydroprocessing catalyst may have anaverage cross-sectional dimension of from 0.01 millimeters (mm) to 5.0mm, from 0.1 mm to 5.0 mm, from 0.5 mm to 5.0 mm, from 0.01 mm to 3.0mm, from 0.1 mm to 3.0 mm, from 0.5 mm to 3.0 mm, from 0.01 mm to 2.5mm, from 0.1 mm to 2.5 mm, from 0.5 mm to 2.5 mm, from 0.01 mm to 2.0mm, from 0.1 mm to 2.0 mm, or from 0.5 mm to 2.0 mm. The cross-sectionaldimension of the hydroprocessing catalyst may be measured usingTransmission Electron Microscopy (TEM), dry sieving, or the laser lightscattering technique.

As stated previously, the coated hydroprocessing catalyst includes thecatalyst activation agent, a catalyst deactivation agent, or both. Thecatalyst activation agent, a catalyst deactivation agent, or both may beimpregnated or absorbed into the pores of the porous support.

The catalyst activation agent may include a sulfur containing compound.In one embodiment, the catalyst activation agent may include organicsulfide, organic disulfide, organic polysulfide, elemental sulfur, ortheir oxidized forms. For example, the catalyst activation agent mayinclude methanethiol, thiophene, dialkyl disulfide, diaryl disulfide, orcombinations thereof. The catalyst activation agent may include dimethyldisulfide (DMDS). The catalyst activation agent may include disulfideoil from a Mercaptan Oxidation (Merox) unit. The disulfide oil from theMerox unit may have a general formula R S S R′, wherein R and R′ arealkyl groups with carbon number in the range 1 to 20. In someembodiments, the general formula may include DMDS.

The catalyst deactivation agent may include a nitrogen containingcompound. In one embodiment, the catalyst deactivation agent may includean organic nitrogen compound. For example, the catalyst deactivationagent may include amine, carbazole, indoles, quinoline, amide, acridine,aniline, ammonia, or their oxidized forms. The catalyst deactivationagent may include methyldiethanolamine (MDEA).

The coated hydroprocessing catalyst may also include the coating layer.The coating layer may encapsulate the catalyst activation agent, thecatalyst deactivation agent, or both within the hydroprocessingcatalyst.

The coating layer may include polymer, paraffinic oil, or both. In oneor more embodiments, the polymer may include a polymer materialoriginates from olefins, carbonates, aromatics, sulfones, fluorinatedhydrocarbons, chlorinated hydrocarbons, acrylonitrides, or combinationsthereof. The polymer material may include polystyrene, polyethylene,polypropylene, or combinations thereof. In one or more embodiments, theparaffinic oil may include N-paraffinic wax with carbon number 20 to 50.

In one or more embodiments, the coating layer may have an averagethickness from 50 μm to 100 μm, from 50 μm to 90 μm, from 50 μm to 80μm, from 40 μm to 100 μm, from 40 μm to 90 μm, or from 40 μm to 80 μm.

In one or more embodiments, the coating layer may have a melting pointof up to 350° C., from 20° C. to 350° C., from 30° C. to 350° C., from40° C. to 350° C., from 50° C. to 350° C., from 100° C. to 350° C., from20° C. to 300° C., from 30° C. to 300° C., from 40° C. to 300° C., from50° C. to 300° C., from 100° C. to 300° C., from 20° C. to 250° C., from30° C. to 250° C., from 40° C. to 250° C., from 50° C. to 250° C., orfrom 100° C. to 250° C.

In one or more embodiments, the coated hydroprocessing catalyst may havean average cross-sectional dimension of from 0.05 mm to 6.0 mm, from0.06 mm to 6.0 mm, from 0.1 mm to 6.0 mm, from 0.5 mm to 6.0 mm, from0.05 mm to 3.0 mm, from 0.06 mm to 3.0 mm, from 0.1 mm to 3.0 mm, orfrom 0.5 mm to 3.0 mm.

Methods of Producing Encapsulated Hydroprocessing Catalyst

Further embodiments of the present disclosure are directed to methods ofthe above-referenced encapsulated hydroprocessing catalyst (coatedhydroprocessing catalyst). As described above, encapsulatedhydroprocessing catalyst may be produced by coating the hydroprocessingcatalyst to encapsulate the catalyst activation precursor, the catalystdeactivation precursor, or both onto the pores of the hydroprocessingcatalyst. The encapsulated hydroprocessing catalysts produced by coatingthe hydroprocessing catalyst with the polymer or the paraffinic oilallows for preparation of hydroprocessing catalyst having improvedcatalytic activity without excess supply of the catalyst activationprecursor, the catalyst deactivation precursor, or both. Without beingbound by theory, encapsulating the hydroprocessing catalyst with acoating layer reduces the need for supplemental catalyst deactivationagent, because the coating layer slows the desorption or decompositionof the catalyst deactivation agent loaded on the porous support.

The method may include preparing the hydroprocessing catalyst thatincludes the above described porous support and at least one metalsupported on the porous support. Referring to FIGS. 1 and 2 , thepreparing step may include preparing the binder 110 and preparing atleast one of alumina, silica, titania, or combinations thereof. Thebinder may be mixed with the at least one of alumina, silica, titania,or combinations thereof, to produce the blend. The binder may be capableof holding the hydroprocessing catalyst components together. Variousbinders are considered suitable. For example, the binder may includeclay, mineral, alumina, silica, titania, or combinations thereof. Theclay may include kaolin. The alumina may include one or more ofattapulgite, boehmite, or partially acid-peptized alumina.

In some embodiments, prior to mixing at least one of alumina, silica,titania, or combinations thereof with the binder, the zeolite may beprepared 120 and mixed 200 with the blend including at least one ofalumina, silica, titania, or combinations thereof and the binder. Inalternative embodiments, the zeolite may be added with at least one ofalumina, silica, titania, or combinations thereof.

Still referring to FIGS. 1 and 2 , in some embodiments, the blend may beextruded 300 to produce the catalyst particle that includes zeolite,alumina, silica, titania, or combinations thereof. In other embodiments,the catalyst particle may be produced through spray drying, pelletizing,agglomeration, oil drop, or combinations thereof. In some embodiments,producing the catalyst particle may include producing the poroussupport. The porous support may be produced through precipitation,mulling, kneading 200, or combinations thereof. The mulled or kneadedsupport may be subjected to the thermal treatment at a temperature offrom 10° C. to 50° C., from 10° C. to 40° C., from 20° C. to 50° C., orfrom 20° C. The at least one metal may be added to the porous support bymixing or impregnation to produce the catalyst particle. For example,the at least one metal may be introduced to the porous support bymixing, and may be converted to an oxide form in-situ by calcination.Alternatively, the at least one metal in oxide form may be introduced tothe porous support by mixing to produce the catalyst particle.

The catalyst particle may be calcined 400 to produce the calcinedcatalyst particle. Calcination temperature may range from 500° C. to650° C., or from 500° C. to 600° C. Calcination times may range from 0.5hours to 6 hours, from 0.5 hours to 3 hours, from 1 hour to 6 hours, orfrom 1 hour to 3 hours. The calcination step 400 may be carried out inan oxygen containing atmosphere.

The calcined catalyst particle may be impregnated 500 with the at leastone metal to produce the impregnated catalyst particle. The impregnationstep 500 described in this disclosure is based on incipient wetnessimpregnation of the at least one metal. Other methods of impregnating500 the calcined catalyst particle with the at least one metal, such asimmersion impregnation, evaporative impregnation, may also be employed.

The calcined catalyst particle may be contacted with the solution thatincludes the at least one metal. As stated previously, the at least onemetal may include the IUPAC Groups 6, 9 and 10 metals. In someembodiments, the IUPAC Groups 6, 9 and 10 metals may include Co, Mo, Ni,W, or combinations thereof. In one embodiment, the at least one metalmay be in oxide form, such as CoO, MoO₃, NiO, WO₃. In other embodiment,the at least one metal may be in sulfide form, such as Co₉S₈, MoS₂,Ni₃S₂, WS₂.

The calcined catalyst particle may be contacted with the solution atambient conditions. The solution may be mixed for a period of time priorto contacting the calcined catalyst particle with the solution. Aftercontacting the calcined catalyst particle with the solution includingthe at least one metal, the excess liquids, such as solution or solvent,may be removed from the mixture to produce the impregnated catalystparticle. Removing the liquid components may include removing the excesssolution from the impregnated catalyst particle and drying theimpregnated catalyst particle. Removing the excess solution from theimpregnated catalyst particle may include subjecting the mixture todecantation, filtration, vacuum filtration, or combinations thereof. Insome embodiments, drying may be conducted at a temperature of from 50°C. to 200° C., from 50° C. to 180° C., from 50° C. to 150° C., from 100°C. to 200° C., from 100° C. to 180° C. or from 100° C. to 150° C. Thedrying period may be from 3 hours to 30 hours, from 3 hours to 20 hours,or from 3 hours to 10 hours.

In one or more embodiments, impregnating 500 the calcined catalystparticle may take place at a temperature of from 20° C. to 40° C., from20° C. to 35° C., or from 20° C. to 30° C. In one or more embodiments,impregnating 500 the calcined catalyst particle may take place atpressure of from 0.5 bars to 3 bars, from 0.5 bars to 2.5 bars, from 1bar to 3 bars, from 1.5 bar to 2.5 bars, from 1.5 bars to 3 bars, orfrom 1.5 bars to 2.5 bars.

The impregnated catalyst particle may be calcined 600 to produce thehydroprocessing catalyst. Calcination temperature may range from 500° C.to 700° C., from 500° C. to 650° C., or from 500° C. to 600° C.Calcination times may range from 0.5 hours to 6 hours, from 0.5 hours to5 hours, from 0.5 hours to 3 hours, from 1 hour to 6 hours, from 1 hourto 5 hours, or from 1 hour to 3 hours. The calcination step 600 may becarried out in an oxygen containing atmosphere.

The method may further include applying the catalyst activationprecursor, the catalyst deactivation precursor, or both onto pores ofthe hydroprocessing catalyst to form a loaded hydroprocessing catalyst.In some embodiments, the catalyst activation precursor, the catalystdeactivation precursor, or both may be loaded inside the pores of theporous support, on the surface of the porous support, or both. Once thecatalyst activation precursor and the catalyst deactivation precursor isloaded inside the pores of the porous support, on the surface of theporous support, or both, the catalyst activation precursor and thecatalyst deactivation precursor may constitute the catalyst activationagent and the catalyst deactivation agent, respectively.

The catalyst activation precursor, the catalyst deactivation precursor,or both may be applied for a period of time long enough to providesufficient adsorption or deposition of the catalyst activationprecursor, the catalyst deactivation precursor, or both inside the poresof the porous support, on the surface of the porous support, or both. Insome embodiments, the catalyst activation precursor, the catalystdeactivation precursor, or both may be applied in gas phase, liquidphase, or gas-liquid phase.

Still referring to FIGS. 1 and 2 , in one or more embodiments, theapplying step may include impregnating 700 the catalyst activationprecursor, the catalyst deactivation precursor, or both into thehydroprocessing catalyst to produce the loaded hydroprocessing catalyst.The applying steps described in this disclosure are based on incipientwetness impregnation of the catalyst activation precursor, the catalystdeactivation precursor, or both inside the pores of the porous support,on the surface of the porous support, or both. Other methods ofimpregnating 700 the catalyst activation precursor, the catalystdeactivation precursor, or both into the hydroprocessing catalyst, suchas immersion impregnation, evaporative impregnation, may also beemployed.

The impregnation step 700 may include contacting the hydroprocessingcatalyst with the solution that includes the catalyst activationprecursor, the catalyst deactivation precursor, or both. As statedpreviously, the catalyst activation precursor may include a sulfurcontaining compound. In one embodiment, the catalyst activationprecursor may include organic sulfide, organic disulfide, organicpolysulfide, elemental sulfur, or their oxidized forms. For example, thecatalyst activation precursor may include methanethiol, thiophene,dialkyl disulfide, diaryl disulfide, or combinations thereof. Thecatalyst activation precursor may include dimethyl disulfide (DMDS). Thecatalyst activation precursor may include disulfide oil from a Meroxunit. The disulfide oil from the Merox unit may have a general formula RS S R′, wherein R and R′ are alkyl groups with carbon number in therange 1 to 20. In some embodiments, the general formula may includeDMDS. The catalyst deactivation precursor may include a nitrogencontaining compound. In one embodiment, the catalyst deactivationprecursor may include an organic nitrogen compound. For example, thecatalyst deactivation precursor may include amine, carbazole, indoles,quinoline, amide, acridine, aniline, ammonia, or their oxidized forms.The catalyst deactivation precursor may include methyldiethanolamine(MDEA).

In one or more embodiments, the impregnation step 700 may take place attemperature of from 20 Celsius (° C.) to 80° C., from 20° C. to 75° C.,from 20 to 70° C., from 25° C. to 80° C., from 25° C. to 75° C., from 25to 70° C., from 30° C. to 80° C., from 30° C. to 75° C., or from 30° C.to 70° C. In one or more embodiments, the impregnation step 700 may takeplace at pressure of from 1 bar to 3 bars, from 1 bar to 2.5 bars, from1 bar to 2 bars, from 1.5 bars to 3 bars, 1.5 bars to 2.5 bars, or from1.5 bars to 2 bars.

The hydroprocessing catalyst may be contacted with the solution atambient conditions. The solution may be mixed for a period of time priorto contacting the hydroprocessing catalyst with the solution. Themixture comprising the hydroprocessing catalyst dispersed in thesolution may be mixed for a period of time long enough to providesufficient adsorption or deposition of the catalyst activationprecursor, the catalyst deactivation precursor, or both, inside thepores of the porous support, on the surface of the porous support, orboth.

After contacting the hydroprocessing catalyst with the solutionincluding the catalyst activation precursor, the catalyst deactivationprecursor, or both, the excess liquids, such as solution or solvent, maybe removed from the mixture to produce the loaded hydroprocessingcatalyst. Removing the liquid components may include removing the excesssolution from the loaded hydroprocessing catalyst and drying the loadedhydroprocessing catalyst. Removing the excess solution from the loadedhydroprocessing catalyst may include subjecting the mixture todecantation, filtration, vacuum filtration, or combinations thereof. Insome embodiments, drying may be conducted at a temperature of from 50°C. to 200° C., from 50° C. to 180° C., from 100° C. to 200° C., or from100° C. to 180° C. The drying period may be from 3 hours to 30 hours,from 3 hours to 20 hours, or from 3 hours to 10 hours.

In some embodiments, the applying step may include spraying the catalystactivation precursor, the catalyst deactivation precursor, or both overthe hydroprocessing catalyst. For example, the catalyst activationprecursor, the catalyst deactivation precursor, or both may be sprayedover the hydroprocessing catalyst in a conveyor belt. In one or moreembodiments, the applying step may include pouring the catalystactivation precursor, the catalyst deactivation precursor, or both overthe hydroprocessing catalyst. In one or more embodiments, the applyingstep may include immersing the hydroprocessing catalyst into thecatalyst activation precursor, the catalyst deactivation precursor, orboth. Immersed hydroprocessing catalyst may be drained. In one or moreembodiments, the applying step may include soaking the hydroprocessingcatalyst into the catalyst activation precursor, the catalystdeactivation precursor, or both. Soaked hydroprocessing catalyst may bedrained.

In some embodiments, when the catalyst activation precursor is loadedinside the pores of the hydroprocessing catalyst, onto the surface ofthe hydroprocessing catalyst, or both, the at least one metal includedin the hydroprocessing catalyst may be a sulfide to maximizehydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrocracking(HCR), hydrogenation (HYD) or hydrodemetallization (HDM) functionality.The sulfidation treatment may be carried out in-situ or ex-situ. In-situsulfidation may be conducted by treating the at least one metal in oxideform with the catalyst activation precursor in the presence of hydrogen.The catalyst activation precursor may generate hydrogen sulfide, whichconverts the metal oxide to metal sulfide, such as Co₉S₈, MoS₂, Ni₃S₂,WS₂. In some embodiments, in-situ sulfidation may be carried out under ahydrogen pressure. In one or more embodiments, in-situ sulfidation maybe carried out at a temperature of from 20° C. to 250° C., from 20° C.to 200° C., from 30° C. to 250° C., or from 30° C. to 200° C. In one ormore embodiments, ex-situ sulfidation may be conducted by providingorganic polysulfide as a catalyst activation precursor. Organicpolysulfide may include are dialkyl-polysulfides with a formula R-Sn—R′,wherein R and R′ are alkyls containing a carbon number in the range of 1to 20, and n is a number in range of 3 to 10. In some embodiments,organic polysulfide may include Di-tert-butyl polysulfide (TBPS 454). Inother embodiments, the hydroprocessing catalyst may be impregnated withelemental sulfur at a temperature below the melting point of sulfur. Atthe conditions, sulfur may sublime and be substantially incorporatedinto the pores of the hydroprocessing catalyst. The sulfur impregnatedcatalyst may be contacted with a hydrocarbon solvent to pre-wet mixtureand react with to convert metal oxides to metal sulfides.

In some embodiments, when the catalyst deactivation precursor is loadedinside the pores of the hydroprocessing catalyst, onto the surface ofthe hydroprocessing catalyst, or both, the catalyst deactivationprecursor may moderate the activity of the hydroprocessing catalyst. Insome embodiments, nitrogen may be injected into a reactor in the form ofaqueous or anhydrous ammonia to moderate the activity of thehydroprocessing catalyst. In some embodiments, to minimize the hazardsof high-pressure ammonia injection, such as leaking or spilling ammoniafrom a tank or pipe, the catalyst deactivation precursor may includemethyldiethanolamine (MDEA). For example, when injected into the reactorat the temperature above 180° C. in the presence of hydrogen, amines mayreadily decompose to form ammonia needed to deactivate thehydroprocessing catalyst.

Referring to FIG. 2 , the method further includes coating 710 the loadedhydroprocessing catalyst with a coating material to produce theencapsulated hydroprocessing catalyst 800. Coating 710 the loadedhydroprocessing catalyst with the coating material that includes thepolymer or the paraffinic oil may produce the coating layer on theloaded hydroprocessing catalyst. As stated previously, the polymer mayinclude a polymer material originating from olefins, carbonates,aromatics, sulfones, fluorinated hydrocarbons, chlorinated hydrocarbons,acrylonitrides, or combinations thereof. The polymer material mayinclude polystyrene, polyethylene, polypropylene, or combinationsthereof. The paraffinic oil may include N-paraffinic wax with carbonnumber 20 to 50.

Coating 710 the loaded hydroprocessing catalyst may be conducted throughspraying the coating material onto the loaded hydroprocessing catalyst.

In some embodiments, the coating layer may fully surround the loadedhydroprocessing catalyst. The coating layer may fully surround thehydroprocessing catalyst, the catalyst activation precursor, thecatalyst deactivation precursor, or combinations thereof.

In one or more embodiments, the coating layer may have an averagethickness from 50 μm to 100 μm, from 50 μm to 90 μm, from 50 μm to 80μm, from 40 μm to 100 μm, from 40 μm to 90 μm, or from 40 μm to 80 μm.

EXAMPLES

The following examples illustrate one or more additional features of thepresent disclosure. It should be understood that these examples are notintended to limit the scope of the disclosure or the appended claims inany manner.

Example 1 Hydroprocessing Catalyst

The hydroprocessing catalyst was prepared from 30 wt. % of zeolite and70 wt. % of binder. USY zeolite having a FAU type framework was used asthe zeolite and alumina was used as the binder. The zeolite and binderwere mixed to form a support. The support was mixed with 4 wt. % nickeland 16 wt. % molybdenum based on the total amount of the supportrespectively. The mixture was extruded and dried at 130° C. for 20hours, and then calcined at 600° C. for 1 hour to produce thehydroprocessing catalyst.

Example 2 DMDS Loaded Hydroprocessing Catalyst

The hydroprocessing catalyst was dried in an oven for 1 hour at 150° C.to remove any volatile matters. As a catalyst activation precursor,aliquots of Dimethyl disulfide (DMDS) was added to 2.5 grams (g) of thedried hydroprocessing catalyst. 1.6 g of DMDS was absorbed into thepores of the hydroprocessing catalyst to produce the loadedhydroprocessing catalyst.

Example 3 TGA of DMDS Loaded Hydroprocessing Catalyst

10 mg of the loaded hydroprocessing catalyst was analyzed byThermogravimetric analysis (TGA) under air flow. The TGA data wereobtained on TA Instruments (Model number TGA Q500), 20° C./min heatingrate over the range of from 25 to 900° C. As shown in FIG. 3 , only 1wt. % of DMDS based on the total amount of DMDS and hydroprocessingcatalyst was released at 50° C., 5 wt. % was released at 100° C. andthen 10 to 12 wt. % of DMDS was released from the loaded hydroprocessingcatalyst at 300° C. The curve was flat after 300° C., indicating thatall the DMDS was desorbed and/or decomposed under air flow.

Example 4 Encapsulated DMDS Loaded Hydroprocessing Catalyst (CoatedHydroprocessing Catalyst)

0.26 grams of n-paraffinic wax used to coat 4.1 grams the DMDS loadedhydroprocessing catalyst. The coating layer encapsulated the DMDS ontothe pores of the loaded hydroprocessing catalyst.

Example 5 TBA Loaded Hydroprocessing Catalyst

The hydroprocessing catalyst was dried in an oven for 1 hour at 150° C.to remove any volatile matters. As a catalyst activation precursor,aliquots of t-butylamine (TBA) was added to 6.4 grams (g) of the driedhydroprocessing catalyst. 2.5 g of TBA was absorbed into the pores ofthe hydroprocessing catalyst to produce the loaded hydroprocessingcatalyst.

Example 6 TGA of TBA Loaded Hydroprocessing Catalyst

In Example 6, 40.35 mg of the loaded hydroprocessing catalyst of Example5 was analyzed by TGA under air flow. The TGA data were obtained on TAInstruments (Model number TGA Q500), 20° C./min heating rate over therange of from 25 to 900° C. As shown in FIG. 4 , only 0.94 wt. % of TBAbased on the total amount of TBA and hydroprocessing catalyst wasreleased at 50° C., 4.4 wt. % was released at 100° C. and then 13 to 14wt. % of TBA was released from the loaded hydroprocessing catalyst at310° C. The curve was flat after 310° C., indicating that all the TBAwas desorbed and/or decomposed under air flow.

Example 7 Encapsulated TBA Loaded Hydroprocessing Catalyst (CoatedHydroprocessing Catalyst)

In Example 7, 0.8 g of n-paraffinic wax used to coat 15.9 g of TBAloaded hydroprocessing catalyst. The coating layer encapsulated the TBAonto the pores of the loaded hydroprocessing catalyst.

Example 8 TGA of Encapsulated Loaded Hydroprocessing Catalyst

In Example 8, 40.35 mg of the encapsulated hydroprocessing catalyst ofExample 7 was analyzed by TGA under air flow. The TGA data were obtainedon TA Instruments (Model number TGA Q500), 20° C./min heating rate overthe range of from 25 to 900° C. As shown in FIG. 4 , only 0.21 wt. % ofTBA based on the total amount of TBA, hydroprocessing catalyst, andn-paraffin wax was released at 50° C., 0.81 wt. % was released at 100°C. and then 15.0 wt. % of TBA and paraffinic wax were released from thecoated hydroprocessing catalyst at around 650° C. The curve was flatafter 650° C., indicating that all the TBA and wax were desorbed and/ordecomposed under air flow.

A first aspect of the present disclosure may be directed to a method ofproducing an encapsulated hydroprocessing catalyst, the methodcomprising preparing a hydroprocessing catalyst comprising a poroussupport and at least one metal supported on the porous support, theporous support comprising alumina, silica, titania, or combinationsthereof, and the at least one metal selected from IUPAC Groups 6, 9 and10 metals; applying a catalyst activation precursor comprising a sulfurcontaining compound, a catalyst deactivation precursor comprising anitrogen containing compound, or both onto pores of the hydroprocessingcatalyst to form a loaded hydroprocessing catalyst; and coating theloaded hydroprocessing catalyst with a coating material to produce theencapsulated hydroprocessing catalyst, wherein the coating materialcomprises a polymer or a paraffinic oil.

A second aspect of the present disclosure may include the first aspect,wherein the catalyst activation precursor, the catalyst deactivationprecursor, or both are loaded inside the pores of the porous support, ona surface of the support, or both.

A third aspect of the present disclosure may include either one of thefirst or second aspects, wherein the applying step comprises:impregnating the catalyst activation precursor, the catalystdeactivation precursor, or both into the hydroprocessing catalyst; oradsorbing the catalyst activation precursor, the catalyst deactivationprecursor, or both into the hydroprocessing catalyst.

A fourth aspect of the present disclosure may include any one of thefirst through third aspects, wherein the impregnating process comprisesimmersion impregnation, incipient wetness impregnation, or evaporativeimpregnation.

A fifth aspect of the present disclosure may include any one of thefirst through fourth aspects, wherein the applying step comprises:spraying the catalyst activation precursor, the catalyst deactivationprecursor, or both over the hydroprocessing catalyst; pouring thecatalyst activation precursor, the catalyst deactivation precursor, orboth over the hydroprocessing catalyst; immersing the hydroprocessingcatalyst into the catalyst activation precursor, the catalystdeactivation precursor, or both; or soaking the hydroprocessing catalystinto the catalyst activation precursor, the catalyst deactivationprecursor, or both.

A sixth aspect of the present disclosure may include any one of thefirst through fifth aspects, wherein the catalyst activation precursor,the catalyst deactivation precursor, or both is loaded in gas phase,liquid phase, or gas-liquid phase.

A seventh aspect of the present disclosure may include any one of thefirst through sixth aspects, wherein the applying step takes place at atemperature of from 20° C. to 80° C.

An eighth aspect of the present disclosure may include any one of thefirst through seventh aspects, wherein the applying step takes place ata pressure of from 1 bar to 3 bars.

A ninth aspect of the present disclosure may include any one of thefirst through eighth aspects, wherein the preparing step comprises:mixing at least one of an alumina, a silica, or a titania with a binderto produce a blend; extruding the blend into a catalyst particle;calcining the catalyst particle to produce the calcined catalystparticle; impregnating the calcined catalyst particle with the at leastone metal to produce an impregnated catalyst particle; and calcining theimpregnated catalyst particle to produce the hydroprocessing catalyst.

A tenth aspect of the present disclosure may include any one of thefirst through ninth aspects, further comprising adding a zeolite to theblend prior to extruding the blend.

An eleventh aspect of the present disclosure may include any one of thefirst through tenth aspects, wherein the zeolite has a FAU, MFI, MOR, orBEA type framework.

A twelfth aspect of the present disclosure may include any one of thefirst through eleventh aspects, wherein the at least one metal is inoxide form or sulfide form.

A thirteenth aspect of the present disclosure may include any one of thefirst through twelfth aspects, wherein the IUPAC Groups 6, 9 and 10metals comprise Co, Mo, Ni, W, or combinations thereof.

A fourteenth aspect of the present disclosure may include any one of thefirst through thirteenth aspects, wherein the hydroprocessing catalysthas an average cross-sectional dimension of from 0.01 mm to 5.0 mm.

A fifteenth aspect of the present disclosure may include any one of thefirst through fourteenth aspects, wherein the catalyst activationprecursor comprises organic sulfide, organic disulfide, organicpolysulfide, elemental sulfur, or their oxidized forms.

A sixteenth aspect of the present disclosure may include any one of thefirst through fifteenth aspects, wherein the catalyst activationprecursor comprises methanethiol, thiophene, dialkyl disulfide, diaryldisulfide, or combinations thereof.

A seventeenth aspect of the present disclosure may include any one ofthe first through sixteenth aspects, wherein the catalyst activationprecursor comprises dimethyl disulfide (DMDS).

An eighteenth aspect of the present disclosure may include any one ofthe first through seventeenth aspects, wherein the catalyst deactivationprecursor comprises an organic nitrogen compound.

A nineteenth aspect of the present disclosure may include any one of thefirst through eighteenth aspects, wherein the catalyst deactivationprecursor comprises amine, carbazole, indoles, quinoline, amide,acridine, aniline, ammonia, or their oxidized forms.

A twentieth aspect of the present disclosure may include any one of thefirst through nineteenth aspects, wherein the catalyst deactivationprecursor comprises methyldiethanolamine (MDEA).

It is noted that one or more of the following claims utilize the term“wherein”, “where” or “in which” as a transitional phrase. For thepurposes of defining the present technology, it is noted that this termis introduced in the claims as an open-ended transitional phrase that isused to introduce a recitation of a series of characteristics of thestructure and should be interpreted in like manner as the more commonlyused open-ended preamble term “comprising.” For the purposes of definingthe present technology, the transitional phrase “consisting of” may beintroduced in the claims as a closed preamble term limiting the scope ofthe claims to the recited components or steps and any naturallyoccurring impurities. For the purposes of defining the presenttechnology, the transitional phrase “consisting essentially of” may beintroduced in the claims to limit the scope of one or more claims to therecited elements, components, materials, or method steps as well as anynon-recited elements, components, materials, or method steps that do notmaterially affect the novel characteristics of the claimed subjectmatter. The transitional phrases “consisting of” and “consistingessentially of” may be interpreted to be subsets of the open-endedtransitional phrases, such as “comprising” and “including,” such thatany use of an open ended phrase to introduce a recitation of a series ofelements, components, materials, or steps should be interpreted to alsodisclose recitation of the series of elements, components, materials, orsteps using the closed terms “consisting of” and “consisting essentiallyof.” For example, the recitation of a composition “comprising”components A, B, and C should be interpreted as also disclosing acomposition “consisting of” components A, B, and C as well as acomposition “consisting essentially of” components A, B, and C. Anyquantitative value expressed in the present application may beconsidered to include open-ended embodiments consistent with thetransitional phrases “comprising” or “including” as well as closed orpartially closed embodiments consistent with the transitional phrases“consisting of” and “consisting essentially of.”

As used in the Specification and appended Claims, the singular forms“a”, “an”, and “the” include plural references unless the contextclearly indicates otherwise. The verb “comprises” and its conjugatedforms should be interpreted as referring to elements, components orsteps in a non-exclusive manner. The referenced elements, components orsteps may be present, utilized or combined with other elements,components or steps not expressly referenced.

Further, when an amount, concentration, or other value or parameter isgiven as either a range, preferred range or a list of upper preferablevalues and lower preferable values, this is to be understood asspecifically disclosing all ranges formed from any pair of any upperrange limit or preferred value and any lower range limit or preferredvalue, regardless of whether ranges are separately disclosed. Where arange of numerical values is recited herein, unless otherwise stated,the range is intended to include the endpoints thereof, and all integersand fractions within the range. It is not intended that the scope of theinvention be limited to the specific values recited when defining arange. When a component is indicated as present in a range starting from0, such component is an optional component (i.e., it may or may not bepresent). When present, an optional component may be at least 0.1 weight% of the composition or copolymer.

When materials, methods, or machinery are described herein with the term“known to those of skill in the art”, “conventional” or a synonymousword or phrase, the term signifies that materials, methods, andmachinery that are conventional at the time of filing the presentapplication are encompassed by this description.

It should be understood that any two quantitative values assigned to aproperty may constitute a range of that property, and all combinationsof ranges formed from all stated quantitative values of a given propertyare contemplated in this disclosure. The subject matter of the presentdisclosure has been described in detail and by reference to specificembodiments. It should be understood that any detailed description of acomponent or feature of one or more embodiments does not necessarilyimply that the component or feature is essential to the particularembodiment or to any other embodiment. Further, it should be apparent tothose skilled in the art that various modifications and variations canbe made to the described embodiments without departing from the spiritand scope of the claimed subject matter.

What is claimed is:
 1. A method of producing an encapsulatedhydroprocessing catalyst comprises: preparing a hydroprocessing catalystcomprising a porous support and at least one metal supported on theporous support, the porous support comprising alumina, silica, titania,or combinations thereof, and the at least one metal selected fromInternational Union of Pure and Applied Chemistry (IUPAC) Groups 6, 9and 10 metals, wherein the porous support further comprises a zeolitehaving a FAU, MFI, MOR, or BEA type framework; applying a catalystactivation precursor comprising a sulfur containing compound, a catalystdeactivation precursor comprising a nitrogen containing compound, orboth onto pores of the hydroprocessing catalyst to form a loadedhydroprocessing catalyst; and coating the loaded hydroprocessingcatalyst with a coating material to produce the encapsulatedhydroprocessing catalyst, wherein the coating material comprises apolymer or a paraffinic oil.
 2. The method of claim 1, wherein thecatalyst activation precursor, the catalyst deactivation precursor, orboth are loaded inside the pores of the porous support, on a surface ofthe support, or both.
 3. The method of claim 1, wherein the applyingstep comprises: impregnating the catalyst activation precursor, thecatalyst deactivation precursor, or both into the hydroprocessingcatalyst; or adsorbing the catalyst activation precursor, the catalystdeactivation precursor, or both into the hydroprocessing catalyst. 4.The method of claim 3, wherein the impregnating process comprisesimmersion impregnation, incipient wetness impregnation, or evaporativeimpregnation.
 5. The method of claim 1, wherein the applying stepcomprises: spraying the catalyst activation precursor, the catalystdeactivation precursor, or both over the hydroprocessing catalyst;pouring the catalyst activation precursor, the catalyst deactivationprecursor, or both over the hydroprocessing catalyst; immersing thehydroprocessing catalyst into the catalyst activation precursor, thecatalyst deactivation precursor, or both; or soaking the hydroprocessingcatalyst into the catalyst activation precursor, the catalystdeactivation precursor, or both.
 6. The method of claim 1, wherein thecatalyst activation precursor, the catalyst deactivation precursor, orboth is loaded in a gas phase, liquid phase, or gas-liquid phase.
 7. Themethod of claim 1, wherein the applying step takes place at atemperature of from 20 Celsius (° C.) to 80° C.
 8. The method of claim1, wherein the applying step takes place at a pressure of from 1 bar to3 bars.
 9. The method of claim 1, wherein the preparing step comprises:mixing at least one of an alumina, a silica, or a titania with a binderto produce a blend; extruding the blend into a catalyst particle;calcining the catalyst particle to produce the calcined catalystparticle; impregnating the calcined catalyst particle with the at leastone metal to produce an impregnated catalyst particle; and calcining theimpregnated catalyst particle to produce the hydroprocessing catalyst.10. The method of claim 9, further comprising adding the zeolite to theblend prior to extruding the blend.
 11. The method of claim 1, whereinthe at least one metal is in oxide form or sulfide form.
 12. The methodof claim 1, wherein the IUPAC Groups 6, 9 and 10 metals comprise Co, Mo,Ni, W, or combinations thereof.
 13. The method of claim 1, wherein thehydroprocessing catalyst has an average cross-sectional dimension offrom 0.01 millimeters (mm) to 5.0 mm.
 14. The method of claim 1, whereinthe catalyst activation precursor comprises organic sulfide, organicdisulfide, organic polysulfide, elemental sulfur, or their oxidizedforms.
 15. The method of claim 1, wherein the catalyst activationprecursor comprises methanethiol, thiophene, dialkyl disulfide, diaryldisulfide, or combinations thereof.
 16. The method of claim 1, whereinthe catalyst activation precursor comprises dimethyl disulfide (DMDS).17. The method of claim 1, wherein the catalyst deactivation precursorcomprises an organic nitrogen compound.
 18. The method of claim 1,wherein the catalyst deactivation precursor comprises amine, carbazole,indoles, quinoline, amide, acridine, aniline, ammonia, or their oxidizedforms.
 19. The method of claim 1, wherein the catalyst deactivationprecursor comprises methyldiethanolamine (MDEA).